KR20100016248A - Method and apparatus for measuring ph of low alkalinity solutions - Google Patents
Method and apparatus for measuring ph of low alkalinity solutions Download PDFInfo
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Abstract
Description
본 발명은 일반적으로 pH를 측정하는 시스템, 보다 구체적으로 다수의 pH 지시약 센서로부터의 분광광도적 측정치를 외삽함으로써, 저 알칼리성 용액의 pH를 측정하는 개선된 방법 및 장치에 관한 것이다.The present invention generally relates to a system for measuring pH, and more particularly to improved methods and apparatus for measuring the pH of low alkaline solutions by extrapolating spectrophotometric measurements from multiple pH indicator sensors.
광범위하게 다양한 시스템 및 방법이 수계 시스템의 pH 측정을 위해 사용되어 왔다. 예를 들어, 유리 전극이 실험실 및 산업적인 환경 둘다에서 pH 측정에 통상적으로 사용된다. 선택적으로, 분광광도적 기술이 pH 측정에 사용될 수 있다. pH 측정을 위한 예시적인 시스템 및 방법은 본원과 동일한 양수인에게 양도되고, 이의 개시내용이 본원에 참고로서 혼입되어 있는, 2006년 8월 22일자로 출원된 미국특허출원 제11/507,689호에 기술되어 있다.A wide variety of systems and methods have been used for pH measurement in aqueous systems. For example, glass electrodes are commonly used for pH measurement in both laboratory and industrial environments. Optionally, spectrophotometric techniques can be used for pH measurement. Exemplary systems and methods for pH measurement are described in US patent application Ser. No. 11 / 507,689, filed August 22, 2006, assigned to the same assignee as the present application, the disclosure of which is incorporated herein by reference. have.
종래 기술의 장치 및 시스템이 유용한 제품을 제공하지만, 상대적으로 단순하고 사용자에게 우호적인 방식으로 저 알칼리성 수계 샘플의 신속하고 단순하고 정확한 측정을 제공하는데 완전히 만족스럽지는 않다. 저 알칼리성 용액의 pH를 측정하는 것과 관련된 도전중 하나는 샘플 용액으로의 지시약의 도입에 의해 유도된 pH의 섭동을 무시하지 못한다는 점이다. 이는 사실 지시약 자체가 약한 산 또는 염기이기 때문이다. 달리 말하자면, 약하게 완충된(즉, 저 알칼리성) 용액의 pH는, 샘플내에 도입된 지시약 농도의 양이 용액내의 산 또는 염기의 양에 비해 상당한 점에 기인하여, 심하게 섭동될 수 있다.While prior art devices and systems provide useful products, they are not entirely satisfactory in providing quick, simple and accurate measurements of low alkaline water samples in a relatively simple and user friendly manner. One of the challenges associated with measuring the pH of low alkaline solutions is that the perturbation of pH induced by the introduction of indicators into the sample solution is not negligible. This is because the indicator itself is in fact a weak acid or base. In other words, the pH of a weakly buffered (ie low alkaline) solution may be severely perturbed due to the fact that the amount of indicator concentration introduced into the sample is significant compared to the amount of acid or base in the solution.
종래 기술은 수성 상내의 지시약 유도된 섭동을 (1) 지시약 저장 용액의 pH를 샘플의 pH에 근접하게 조정하고; (2) 샘플 부피에 대한 지시약 첨가의 비를 감소시키고; (3) 단계적인 지시약 첨가를 통한 지시약 유도된 pH 섭동을 관찰한 후, 선형 외삽 방법을 사용하여 샘플의 pH를 수득함으로써 최소화하거나 보정하려는 시도를 하였다. 이러한 종래 기술의 방법은 유용한 결과를 제공할 수 있지만, 전형적으로 시간을 많이 소비하고, 사용자에게 우호적이지 않다. 따라서, 상대적으로 비용면에서 효과적이고 사용자에게 우호적인 방식으로 저 알칼리성 샘플에 대한 정확하고 정밀하고 신속한 pH 측정을 제공하는 개선된 방법 및 시스템에 대한 강한 요구가 여전히 존재한다.Prior art has indicated that indicator induced perturbation in an aqueous phase is controlled by (1) adjusting the pH of the indicator stock solution to be close to the pH of the sample; (2) reducing the ratio of indicator addition to sample volume; (3) After observing the indicator induced pH perturbation through the stepwise addition of the indicator, an attempt was made to minimize or correct by obtaining the pH of the sample using the linear extrapolation method. Such prior art methods can provide useful results, but are typically time consuming and unfriendly to the user. Thus, there is still a strong need for improved methods and systems that provide accurate, precise and rapid pH measurements for low alkaline samples in a relatively cost effective and user friendly manner.
발명의 개요Summary of the Invention
저 알칼리성 용액의 pH를 측정하는 것과 관련된 도전중 하나는 샘플 용액으로의 지시약의 도입에 의해 유도된 pH 값의 섭동을 무시하지 못한다는 점이다. 따라서, pH 측정은 약하게 완충된(즉, 저 알칼리성) 용액에 도입된 지시약 농도에 기인하여 심각하게 섭동될 수 있다. 이러한 도전에 부합하기 위하여, 본 발명은 각 각 상이한 지시약 농도를 갖는 다수의 pH 지시약을 포함하는 센서 어레이(sensor array)를 포함하는 시스템 및 방법을 개시한다. 센서 어레이는 센서 어레이를 공지된 pH를 갖는 샘플 용액에 적용함으로써 보정된다. 각각의 pH 지시약으로부터의 응답은 동시에 기록되고, 보정 함수(즉, 보정 곡선)가 각각의 지시약 농도에서 지시약 농도에 대한 pH 응답을 나타내도록 산출된다. 일단 보정되면, 센서 어레이는 공지되지 않은 pH를 갖는 저 알칼리성 샘플 용액에 적용될 수 있다. 각각의 pH 지시약으로부터의 pH 값으로부터의 결과는 보정 곡선과 비교되고, 각각의 지시약 농도로부터의 pH 응답을 나타내는 피팅 함수(즉, 피팅 곡선)가 산출된다. 이때, 피팅 등식이 산출되고, 외삽되어 공지되지 않은 샘플의 본래(즉, 실제) pH를 수득하기 위한 절편(intercept point)(즉, 지시약 농도가 0인 경우)을 결정한다.One of the challenges associated with measuring the pH of low alkaline solutions is that the perturbation of pH values induced by the introduction of indicators into the sample solution is not negligible. Thus, pH measurements can be severely perturbed due to indicator concentrations introduced in weakly buffered (ie low alkaline) solutions. To meet this challenge, the present invention discloses systems and methods that include a sensor array comprising a plurality of pH indicators, each having a different indicator concentration. The sensor array is calibrated by applying the sensor array to a sample solution having a known pH. The response from each pH indicator is recorded at the same time and a calibration function (ie, calibration curve) is calculated to represent the pH response to the indicator concentration at each indicator concentration. Once calibrated, the sensor array can be applied to low alkaline sample solutions with unknown pH. The results from the pH values from each pH indicator are compared to a calibration curve, and a fitting function (ie fitting curve) representing the pH response from each indicator concentration is calculated. The fitting equation is then calculated and extrapolated to determine the intercept point (ie, when the indicator concentration is zero) to obtain the original (ie, actual) pH of the unknown sample.
본 발명의 다른 양상은 상기 시스템 및 방법의 용도, 및 저 알칼리성 용액의 pH를 측정하는 예시적인 방법에 관한 것이다. 본 발명의 추가의 양상 및 종래 기술에 대한 이점은 첨부된 도면을 참고하여 하기 발명의 상세한 설명 및 첨부된 청구의 범위를 읽음으로써 명백하게 될 것이다.Another aspect of the invention relates to the use of such systems and methods, and to exemplary methods of measuring the pH of low alkaline solutions. Further aspects and advantages of the prior art of the present invention will become apparent by reading the following detailed description of the invention and the appended claims with reference to the accompanying drawings.
도 1은 다양한 약의 티몰 블루의 도입 후 pH의 변화를 나타내는 그래프적 도해이다. 1 is a graphical illustration showing the change in pH after the introduction of thymol blue of various drugs.
도 2는 지시약 첨가 전후의 상이한 용액의 pH 값을 나타내는 일련의 도표이다.2 is a series of plots showing the pH values of different solutions before and after addition of indicator.
도 3은 첨가된 페놀 레드의 양에 대한 pH 측정치 사이의 관계를 도해하는 그래프이다.3 is a graph illustrating the relationship between pH measurements for the amount of phenol red added.
도 4는 4개의 별개의 지시약 농도에서 산출된 보정 곡선을 도해한다.4 illustrates a calibration curve calculated at four separate indicator concentrations.
도 5는 본 발명의 예시적인 선형 외삽 방법으로부터의 결과를 도해하는 그래프이다.5 is a graph illustrating the results from an exemplary linear extrapolation method of the present invention.
본 발명은 저 알칼리성 용액, 예를 들어 저 알칼리성 수계 샘플의 pH를 신속하고 정확하게 측정하기 위한 중합체 필름-기제 센서 어레이를 포함하는 시스템 및 방법을 기술한다. 알칼리성 또는 완충 능력이 수계 샘플의 기본 특성중 하나라는 것은 공지되어 있다. 알칼리성은 산을 중화시키는 용액의 능력의 척도이다. 보다 낮은 알칼리성은 산이 용액에 첨가되는 경우의 pH에 대한 변화에 저항하는 보다 낮은 능력을 의미한다.The present invention describes a system and method comprising a polymer film-based sensor array for quickly and accurately measuring the pH of a low alkaline solution, such as a low alkaline aqueous sample. It is known that alkaline or buffering capacity is one of the basic properties of aqueous samples. Alkaline is a measure of the ability of a solution to neutralize acids. Lower alkalinity means lower ability to resist changes to pH when acid is added to the solution.
본 발명의 개념은 저 알칼리성 용액에서, 샘플로의 지시약의 도입에 의해 유도된 pH의 섭동을 무시하지 못한다는 인식에 기초한다. 이는 사실 지시약 자체가 약한 산 또는 염기이기 때문이다. 따라서, 용액의 pH는, 샘플에 도입된 지시약 농도의 양이 약하게 완충된(즉, 저 알칼리성) 용액내에 존재하는 산 또는 염기의 양에 비해 상당하다는 사실에 기인하여, 심각하게 섭동될 수 있다. 이러한 섭동 효과는 pH 지시약 부하된 필름에서 더욱 더 명백하다.The concept of the present invention is based on the recognition that in low alkaline solutions, the perturbation of pH induced by the introduction of indicator into the sample cannot be ignored. This is because the indicator itself is in fact a weak acid or base. Thus, the pH of the solution can be severely perturbed due to the fact that the amount of indicator concentration introduced into the sample is significant relative to the amount of acid or base present in the weakly buffered (ie low alkaline) solution. This perturbation effect is even more evident in pH indicator loaded films.
상기 도전에 부합하기 위하여, 본 발명의 한 양상은 저 알칼리성 샘플의 pH를 신속하고 정확하게 측정하기 위한 외삽 방법을 기술한다. 상기 방법은 바람직하게는 비제한적으로 본원에 참고로서 혼입된 미국특허출원 제11/507,689호에 따라 구성된 센서 어레이를 이용한다. 이러한 센서 어레이는 각각 상이한 지시약 농도를 갖는 다수의 지시약 부분을 포함하도록 배열된다. 일단 구성되면, 센서 어레이는 샘플의 pH를 분광광도적으로 측정하는데 사용되고, 이에 의해 각각의 지시약은 동시에 별개의 흡광도 pH 측정을 제공한다. 각각의 지시약 부분으로부터 측정된 pH 값을 이들 각각의 지시약 농도에 대해 도표화하고, 측정된 pH 값을 나타내는 피팅 함수(즉, 피팅 등식)를 외삽하고, 지시약 농도가 0인 경우의 절편을 결정하여 샘플의 초기 pH(즉, pH 실제)를 수득한다. 본 발명의 시스템 및 방법은, 지시약 첨가에 의해 야기된 pH 섭동을 최소화하려는 대신에 본 발명은 상이한 지시약 농도로부터의 pH 섭동 사이의 관계를 이용하여 센서 어레이를 보정하고, 이에 따라 공지되지 않은 pH를 갖는 저 알칼리성 샘플로부터의 pH 측정치를 결정하기 위한 기저선 참고 매개변수를 제공하므로, 공지된 방법에 대한 이점을 제공한다.In order to meet this challenge, one aspect of the present invention describes an extrapolation method for quickly and accurately measuring the pH of a low alkaline sample. The method preferably utilizes a sensor array constructed according to, but not limited to, US patent application Ser. No. 11 / 507,689, incorporated herein by reference. Such sensor arrays are arranged to include a plurality of indicator portions each having a different indicator concentration. Once configured, the sensor array is used to spectrophotometrically measure the pH of the sample, whereby each indicator provides a separate absorbance pH measurement at the same time. The pH values measured from each indicator portion are plotted against their respective indicator concentrations, extrapolated to the fitting function representing the measured pH values (i.e., fitting equations), and the intercepts when the indicator concentration is zero are determined to determine the sample. To obtain an initial pH of the pH (ie pH actual). The system and method of the present invention, instead of minimizing the pH perturbation caused by the addition of indicators, uses the relationship between pH perturbations from different indicator concentrations to calibrate the sensor array, thereby reducing the unknown pH. Baseline reference parameters for determining pH measurements from low alkaline samples having are provided, thus providing an advantage over known methods.
본원에 개시된 바와 같이, 본 발명의 시스템 및 방법은 특히 저 알칼리성 용액의 pH를 신속하고 정확하게 결정하는데 구체적으로 매우 적합하다. 저 알칼리성 용액의 pH를 측정하는 것은, 특히 지시약 농도(전형적으로 약한 산 또는 염기임)가 샘플 용액내의 산 또는 염기의 양에 비해 상당한 경우, 용액으로의 약학 산 또는 염기 지시약의 첨가에 의해 유도된 섭동에 기인하여, 간단하지 않다. pH 응답은 열량계, 분광광도계 또는 형광 광도계에 의해 측정될 수 있다.As disclosed herein, the systems and methods of the present invention are particularly well suited, particularly for quickly and accurately determining the pH of low alkaline solutions. Measuring the pH of a low alkaline solution, especially when the indicator concentration (typically a weak acid or base) is significant relative to the amount of acid or base in the sample solution, is induced by the addition of a pharmaceutical acid or base indicator to the solution. Due to perturbation, it is not simple. The pH response can be measured by a calorimeter, spectrophotometer or fluorescence photometer.
본 발명의 예시적인 양태에 따라서, 대체로 필름이 본 발명의 범위를 벗어남이 없이 사용될 수 있는 것으로 이해됨에도 불구하고, pH 센서 어레이는 4개의 필름 어레이로 구성된다. 각각의 센서 필름은 각각 In1, In2, In3 및 In4로 나타내는 상이한 pH 지시약 농도를 함유하였다. 본원에서 예의 목적을 위해서, 각각의 필름의 지시약 농도는 약 0.01 내지 10%의 범위이었다.In accordance with an exemplary embodiment of the present invention, the pH sensor array consists of four film arrays, although it is generally understood that the film can be used without departing from the scope of the present invention. Each sensor film contained different pH indicator concentrations, represented by In 1 , In 2 , In 3, and In 4 , respectively. For purposes of example herein, the indicator concentration of each film ranged from about 0.01 to 10%.
고체 필름은 전형적으로 수용성 중합체, 셀룰로스 아세테이트 또는 폴리 2-하이드록시에틸 메트아크릴레이트(pHEMA)로부터 제조되었다. 지시약은 열량 pH 지시약, 형광 pH 지시약, 또는 당업계에 공지되거나 최근 개발된 다른 적합한 pH 지시약일 수 있다. 열량 pH 지시약은 바람직하게는 페놀 레드, 크레솔 레드, m-크레솔 퍼플, 티몰 블루, 브로모클로로페놀 블루 W.S., 브로모크레솔 그린, 클로로페놀 레드, 브로모크레솔 퍼플, 브로모티몰 블루, 뉴트럴 레드, 페놀프탈레인, o-크레솔프탈레인, 나일 블루 A, 티몰프탈레인, 브로모페놀 블루, 메타크레솔 퍼플, 말라카이트 그린, 브릴리언트 그린, 크리스탈 바이올렛, 메틸 그린, 메틸 바이올렛 2B, 피크르산, 나프톨 옐로우 S, 메탄일 옐로우, 염기성 푹신, 플록신 B, 메틸 옐로우, 메틸 오렌지 및 알리자린으로 이루어진 군으로부터 선택된다.Solid films are typically made from water soluble polymers, cellulose acetates or poly 2-hydroxyethyl methacrylate (pHEMA). The indicator may be a calorific pH indicator, fluorescent pH indicator, or other suitable pH indicator known or recently developed in the art. Calorie pH indicators are preferably phenol red, cresol red, m-cresol purple, thymol blue, bromochlorophenol blue WS, bromocresol green, chlorophenol red, bromocresol purple, bromothymol blue , Neutral red, phenolphthalein, o-cresolphthalein, nile blue A, thymolphthalein, bromophenol blue, metacresol purple, malachite green, brilliant green, crystal violet, methyl green, methyl violet 2B, picric acid, naphthol Yellow S, methanyl yellow, basic fuchsin, phloxine B, methyl yellow, methyl orange and alizarin.
본 발명의 개념을 증명하기 위하여, 본 발명자들은 샘플 용액으로의 상이한 양의 지시약 물질의 첨가에 기인하는, 저 알칼리성 용액에 대한 pH 변화(즉, 섭동)의 이론적인 계산을 수행하였다. 비록 본원에 개시된 예가 본 발명의 넓은 적용성을 증명하도록 포함되었지만, 본원의 예에 개시된 기술이 본 발명자들에 의해 개발된 기술을 나타내고, 이에 따라 이의 실시를 위한 예시적인 방식을 구성하는 것으로 간주될 수 있음이 당업자에게 인정되어야 한다. 그러나, 당업자는 본 발명의 개시내용에 비추어 많은 변화가 개시된 구체적인 양태에 행해질 수 있고, 또한 본 발명의 범위를 벗어남이 없이 동일하거나 유사한 결과가 수득됨을 인정하여야 한다. 그리고, 본원에 개시된 보정 및 외삽 방법은 열량계, 분광광도계 또는 형광 분광계에 의해 측정된 pH 응답과 함께 저 알칼리성 샘플의 pH를 결정하는데 사용될 수 있다.To demonstrate the concept of the present invention, we performed theoretical calculations of the pH change (ie perturbation) for low alkaline solutions due to the addition of different amounts of indicator material to the sample solution. Although the examples disclosed herein have been included to demonstrate the broad applicability of the present invention, the techniques disclosed in the examples herein represent techniques developed by the inventors and therefore should be regarded as constituting exemplary ways for their implementation. It should be appreciated by those skilled in the art that the invention can be made. However, one of ordinary skill in the art should recognize that many changes can be made in the specific embodiments which are disclosed in light of the present disclosure, and that the same or similar results are obtained without departing from the scope of the present invention. And the calibration and extrapolation methods disclosed herein can be used to determine the pH of a low alkaline sample along with the pH response measured by a calorimeter, spectrophotometer or fluorescence spectrometer.
도 1에 도시된 바와 같이, 그래프적 도해는 용액으로의 다양한 양의 티몰 블루의 도입 후에 pH의 변화가 인식되는 방법을 나타낸다. 도 1의 결과는 델타 pH(즉, pH 실제 - pH 측정치)가 용액에 첨가된 지시약 농도가 증가함에 따라 점점 더 커지는 것을 나타낸다. 이러한 결과는 약하게 완충된(즉, 저 알칼리성) 용액이 지시약 첨가에 의해 심각하게 섭동될 수 있음을 명백히 도해한다.As shown in FIG. 1, the graphical illustration shows how changes in pH are recognized after the introduction of various amounts of thymol blue into the solution. The results in FIG. 1 show that the delta pH (ie, pH actual—pH measurement) grows larger as the indicator concentration added to the solution increases. These results clearly illustrate that weakly buffered (ie low alkaline) solutions can be severely perturbed by the addition of indicators.
계속해서 도 1을 참고하면, pH 섭동의 이론적인 계산은 알칼리성이 낮을수록 델타 pH가 커짐을 증명한다. 따라서, 본 발명자들은 지시약을 더욱 첨가하고, 알칼리성을 더욱 낮춤으로써 용액의 pH가 더욱 변화하거나 섭동하는 결과를 추론할 수 있다.With continued reference to FIG. 1, the theoretical calculation of pH perturbation demonstrates that the lower the alkalinity, the higher the delta pH. Therefore, the present inventors can infer the result of further changing or perturbing the pH of the solution by further adding the indicator and lowering the alkalinity.
이러한 결론을 증명하기 위하여, 본 발명자들은 일련의 100ppm 카본에이트 완충액을 사용하고, 지시약 첨가 전후에 상이한 용액의 pH 값을 측정하는 제 1 실험을 수행하였다. 이러한 제 1 실험의 결과는 도 2에 도시되어 있다. 도 2에 도시된 바와 같이, 일련의 도표는 지시약의 첨가 전후에 측정된 상이한 용액의 pH 값을 도해한다. 이러한 결과에 기초하여, 20ppm 페놀 레드(산 형태)가 용액에 첨가되는 경우, pH 측정치가 약간 감소되었음이 명백하다. 도 2는 또한 페놀 레드의 양이 0ppm(다이아몬드 점)에서 100ppm(사각형 점)까지 증가함에 따라 pH의 점진적인 감소가 관찰되었음을 도해한다. 보다 많은 페놀 레드 100ppm이 첨가되는 경우, pH는 크게 섭동되었다. 도 2에 도시된 바와 같이, 100ppm 페놀 레드가 첨가됨에 따라, 약 8.0보다 높은 pH를 갖는 용액이 본질적으로 구별할 수 없게 되었다. 이러한 결과에 기초하여, 지시약 첨가에 의해 유도된 델타 pH의 보정이 설명되어 용액의 실제 pH(pH 실제)를 수득할 수 있음이 명백하게 되었다.To demonstrate this conclusion, we conducted a first experiment using a series of 100 ppm carbonate buffers and measuring the pH values of different solutions before and after the indicator addition. The results of this first experiment are shown in FIG. As shown in FIG. 2, a series of plots illustrate the pH values of different solutions measured before and after addition of the indicator. Based on these results, it is evident that when the 20 ppm phenol red (acid form) was added to the solution, the pH measurement was slightly reduced. 2 also illustrates that a gradual decrease in pH was observed as the amount of phenol red increased from 0 ppm (diamond point) to 100 ppm (square point). When more 100 ppm of phenol red was added, the pH was greatly perturbed. As shown in FIG. 2, as 100 ppm phenol red was added, solutions with pH higher than about 8.0 became essentially indistinguishable. Based on these results, it has become apparent that the correction of the delta pH induced by the indicator addition can be obtained to obtain the actual pH (pH actual) of the solution.
따라서, 본 발명자들은 외삽 방법이 pH를 결정하는데 유용할 수 있음을 나타내는 제 2 실험을 수행하였다. 이러한 제 2 실험에서, 8.12 및 8.53의 본래 pH를 갖는 2개의 100ppm 카본에이트 완충액이 선택되었다. 약 6.8 내지 8.2의 pH 응답 범위를 갖는 지시약 페놀 레드가 사용되었다. 페놀 레드의 산 형태가 약하게 완충된 카본에이트 용액에 단계적으로 첨가되는 경우, pH 미터를 사용하여 용개의 pH를 모니터링하였다.Thus, we conducted a second experiment showing that the extrapolation method may be useful for determining pH. In this second experiment, two 100 ppm carbonate buffers with original pH of 8.12 and 8.53 were selected. Indicator phenol red having a pH response range of about 6.8 to 8.2 was used. When the acid form of phenol red was added stepwise to the weakly buffered carbonate solution, the pH meter was used to monitor the pH of the solution.
도 3에 도시된 바와 같이, 100ppm 지시약 첨가에 대한 pH 측정치의 선형 상관관계가 각각의 100ppm 카본에이트 완충액에 대해 도표화되었다. 각각의 지시약 유형으로부터 측정된 pH를 나타내는 선형 함수를 지시약 백분율이 0이 되는 경우로 외삽하여 절편을 수득하였다. 도 3에 도시된 바와 같이, 절편, 즉 8.13 및 8.46은 지시약 농도가 0인 경우의 용액의 pH를 나타낸다. 이러한 방식에서, 절편은 지시약 첨가 전의 용액의 본래 pH를 나타낸다. 절편이 카본에이트 완충액 각각의 초기 pH 값, 즉 8.12 및 8.53에 매우 근접함은 매우 명백하다. 결과적으로, 본 발명자들의 실험은 지시약 상태에 기인한 pH 섭동이 알칼리성이 매우 낮은 경우에 무시하지 못함을 나타낸다. 또한, 본 발명자들의 실험은 본 발명의 예시적인 선형 외삽 기술이 샘플의 본래 pH를 수득하는데 매우 유용함을 나타낸다. 예시적인 외삽 기술에 사용된 알고리즘은 하기에 더욱 상세히 기술된다.As shown in FIG. 3, the linear correlation of pH measurements for the addition of 100 ppm indicator was plotted for each 100 ppm carbonate buffer. The linear function representing the pH measured from each indicator type was extrapolated to the case where the indicator percentage became zero, to obtain sections. As shown in FIG. 3, the segments, 8.13 and 8.46, represent the pH of the solution when the indicator concentration is zero. In this way, the sections represent the original pH of the solution before the indicator addition. It is very clear that the sections are very close to the initial pH values of the carbonate buffers, namely 8.12 and 8.53. As a result, our experiments show that the pH perturbation due to the indicator state is not negligible when the alkalinity is very low. In addition, our experiments show that the exemplary linear extrapolation technique of the present invention is very useful for obtaining the original pH of a sample. The algorithm used in the exemplary extrapolation technique is described in more detail below.
지시약 첨가에 의해 유도된 pH의 변화를 보정하기 위하여, 일련의 지시약 농도를 갖는 고체 pH 센서에 대해 충분히 높은 알칼리성을 갖는 합성 냉각 표준 용액을 사용하여 보정 곡선을 설정하였다. 이러한 제 3 실험에서, 샘플의 pH는 동일한 고체 pH 센서를 사용하여 측정되었고, 각각의 지시약 농도에 대해 측정된 pH가 계산되었다. 이때, 지시약 농도에 대한 pH 측정치를 도표화하였고, 피팅 등식을 산출하고, 지시약 농도가 0인 경우로 외삽하여 공지되지 않은 샘플의 초기 pH(즉, pH 실제)를 수득하였다.To correct the change in pH induced by the indicator addition, a calibration curve was set using a synthetic cooling standard solution with sufficiently high alkalinity for a solid pH sensor with a series of indicator concentrations. In this third experiment, the pH of the sample was measured using the same solid pH sensor, and the measured pH was calculated for each indicator concentration. At this time, pH measurements for indicator concentrations were plotted, fitting equations were calculated, and extrapolated to the case where the indicator concentration was zero to obtain an initial pH of the unknown sample (ie, pH actual).
도 4에 도시된 바와 같이, 보정 곡선을 4개의 지시약 농도(0.5%, 1.0%, 1.5%, 2.0%)에 대해 산출하였다. 저 알칼리성(100ppm 미만)을 갖는 공지되지 않은 샘플의 pH 값을 측정하였다.As shown in FIG. 4, calibration curves were calculated for four indicator concentrations (0.5%, 1.0%, 1.5%, 2.0%). The pH values of unknown samples with low alkalinity (less than 100 ppm) were measured.
도 5는 본 발명의 예시적인 선형 외삽 방법으로부터의 결과를 도해하는 그래프이다. 도 5로부터 보일 수 있는 바와 같이, 등식의 절편(즉, 지시약 농도가 0인 경우)은 9.18이다. 절편이 지시약 첨가 전의 pH를 나타내므로, 본 발명자들의 외삽 방법은 9.18의 절편이 pH 미터에 의해 측정된 실제 pH 값 9.07에 대한 매우 양호한 근사치임을 증명한다.5 is a graph illustrating the results from an exemplary linear extrapolation method of the present invention. As can be seen from FIG. 5, the intercept of the equation (ie, when the indicator concentration is zero) is 9.18. Since the sections represent the pH before the indicator addition, our extrapolation method demonstrates that the section of 9.18 is a very good approximation to the actual pH value 9.07 measured by the pH meter.
도 4 및 5에 도해된 결과를 달성하기 위하여, pH 센서 어레이는 각각의 센서 필름이 각각 상이한 pH 지시약 농도 In1, In2, In3 및 In4를 함유하는 4개의 필름 어레이로 구성되었다. 이어서, 고정되고 공지된 알칼리성 값을 갖는 일련의 pH 표준 용액으로부터 각각의 pH 센서 필름에 대해 흡광도 응답을 측정하였다.To achieve the results illustrated in FIGS. 4 and 5, the pH sensor array consisted of four film arrays in which each sensor film contained different pH indicator concentrations In 1 , In 2 , In 3 and In 4 , respectively. The absorbance response was then measured for each pH sensor film from a series of pH standard solutions with fixed and known alkaline values.
이어서, 보정 곡선을 상기 제 2 단계로부터 측정된 데이터로부터 각각의 pH 센서 필름에 대해 산출하였다. 보정 함수를 하기 제시된 계산을 위하여 f1, f2, f3 및 f4로 나타냈다.A calibration curve was then calculated for each pH sensor film from the data measured from the second step. The correction functions are represented by f 1 , f 2 , f 3 and f 4 for the calculations presented below.
이어서, 공지되지 않은 pH 샘플을 pH 센서 어레이에 적용하고, 흡광도 값을 각각의 필름으로부터 측정하였다. 하기 제시된 계산을 위하여, 상기 흡광도 값을 필름 1, 2, 3 및 4에 대해 각각 A1, A2, A3 및 A4로 나타냈다.An unknown pH sample was then applied to the pH sensor array and absorbance values were measured from each film. For the calculations presented below, the absorbance values are expressed as A 1 , A 2 , A 3 and A 4 for
이어서, 예비 pH 값을 각각의 상응하는 보정 등식 및 흡광도 값으로부터 각각의 필름에 대해 계산하였다. 예를 들어, 필름 1 내지 4에 대한 pH는 각각 다음과 같이 나타냈다: pH1 = f1(A1), pH2 = f2(A2), pH3 = f3(A3) 및 pH4 = f4(A4). 공지되지 않은 샘플의 알칼리 값이 보정 표준 용액의 알칼리 값과 동일한 경우 상기 pH 값이 모두 동일함에 주의한다. 그러나, 공지되지 않은 샘플의 알칼리 값이 보정 표준 용액의 알칼리 값과 동일하지 않은 경우, pH1, pH2, pH3 및 pH4는 모두 상이한 값을 가질 것이다.Preliminary pH values were then calculated for each film from each corresponding calibration equation and absorbance value. For example, the pHs for the films 1-4 are shown as follows: pH 1 = f 1 (A 1 ), pH 2 = f 2 (A 2 ), pH 3 = f 3 (A 3 ) and pH 4 = f 4 (A 4 ). Note that all pH values are the same if the alkali value of the unknown sample is the same as the alkali value of the calibration standard solution. However, if the alkali value of the unknown sample is not the same as the alkali value of the calibration standard solution, pH 1 , pH 2 , pH 3 and pH 4 will all have different values.
최종 단계에서, 공지되지 않은 샘플에 대한 실제 pH 값은 하기 외삽 알고리즘에 기초하여 예비 pH 값 pH1, pH2, pH3 및 pH4로부터 계산된다:In the final step, the actual pH values for unknown samples are calculated from preliminary pH values pH 1 , pH 2 , pH 3 and pH 4 based on the following extrapolation algorithm:
상기 식에서,Where
i는 필름 지수이고;i is the film index;
Ini는 i 번째 필름의 지시약 농도를 나타내고;In i represents the indicator concentration of the i th film;
pHi는 i 번째 필름의 흡광도 및 상응하는 보정 등식 fi로부터 계산된 겉보기 pH 값이고;pH i is the apparent pH value calculated from the absorbance of the ith film and the corresponding correction equation f i ;
N은 pH 필름의 개수이다.N is the number of pH films.
도 5는 예시적인 외삽 알고리즘의 그래프적 도해이다. 도 5에 제시된 결과에 대한 계산 및 상응하는 수학적인 과정은 하기 수학식에 제시된다:5 is a graphical illustration of an example extrapolation algorithm. The calculations and corresponding mathematical procedures for the results presented in FIG. 5 are shown in the following equation:
따라서, 상기 결과에 기초하여, 본 발명은 다수의 지시약 농도를 갖는 센서 어레이를 제공하고, 공지되지 않은 샘플의 pH 측정치를 공지된 샘플로부터 산출된 보정 곡선으로 보정하여 공지되지 않은 샘플의 pH를 수득함으로써, 저 알칼리성 샘플의 pH를 직접 측정하기 위한 시스템을 제공한다. 본 발명에 따라서, 상기 측정치는 단계적인 지시약 첨가가 포함된 지루하고 오랜 측정 및 계산을 피하기 위한 적시 방식으로 동시에 기록된다. 예를 들어, 본 발명의 예시적인 고체 필름 센서는 동일 반응계(현장) 시험의 경우 약 5분내에 수득되는 결과와 함께 표적에 대한 신속한 응답을 나타냈다.Accordingly, based on the above results, the present invention provides a sensor array having a plurality of indicator concentrations, and correcting pH measurements of unknown samples with calibration curves calculated from known samples to obtain the pH of unknown samples. Thereby providing a system for directly measuring the pH of a low alkaline sample. According to the invention, the measurements are recorded simultaneously in a timely manner to avoid tedious and lengthy measurements and calculations involving stepwise indicator addition. For example, an exemplary solid film sensor of the present invention showed a quick response to the target with results obtained in about 5 minutes for in situ (field) testing.
본원에 기술된 바와 같이, 본 발명의 시스템 및 방법은 일련의 상이한 지시약 농도를 포함하는 고체 중합체-기제 pH 센서 필름 어레이를 혼입한다. 일단 구성되면, 센서 어레이는 공지된 pH 및 알칼리성을 함유하는 샘플 용액에 적용된다. 각각의 지시약 농도로부터의 pH 응답은 동시에 측정되고, 기록된다. 이어서, 보정 함수(즉, 보정 곡선)는 pH 측정치를 각각의 지시약 농도에 대해 도표화함으로써 산출된다. 따라서, 보정 곡선은 지시약 농도에 대한 pH 측정치의 도표를 나타낸다. 이어서, 각각의 pH 측정치를 나타내는 피팅 함수(즉, 피팅 등식)를 산출한다. 피팅 등식은 외삽되어 지시약 농도가 0인 경우의 절편을 결정하고, 이에 따라 지시약 첨가 전의 샘플의 본래 pH의 정확한 지표를 수득한다. 이러한 방식에서, 보정 곡선은 각각의 지시약 부분으로부터의 별개 결과를 보정하여 상이한 지시약 첨가로부터의 pH의 섭동를 저 알칼리성 샘플의 pH를 외삽하기 위하여 신속하고 용이하게 이용할 수 있는 기저선 기준 함수를 나타낸다.As described herein, the systems and methods of the present invention incorporate a solid polymer-based pH sensor film array comprising a series of different indicator concentrations. Once configured, the sensor array is applied to a sample solution containing known pH and alkalinity. The pH response from each indicator concentration is measured and recorded at the same time. The calibration function (ie, calibration curve) is then calculated by plotting pH measurements for each indicator concentration. Thus, the calibration curve represents a plot of pH measurements against indicator concentration. Next, a fitting function (ie, fitting equation) representing each pH measurement is calculated. The fitting equation is extrapolated to determine the section when the indicator concentration is zero, thus obtaining an accurate indication of the original pH of the sample before the indicator addition. In this manner, the calibration curve represents a baseline reference function that can be quickly and easily used to calibrate separate results from each indicator portion to extrapolate the perturbation of pH from different indicator additions to low alkaline samples.
본 개시내용이 전형적으로 예시적인 양태로 설명되고 기술되었지만, 본 개시내용의 범위 및 사상을 어떠한 방식으로든지 벗어나지 않으면서 다양한 개질 및 치환이 행해질 수 있으므로 제시된 상세한 사항을 제한하려는 목적이 아니다. 이와 같이, 본원에 개시된 개시내용의 추가의 개질 및 등가물이 단지 일상적인 실험을 사용하여 당업자에 의해 수행될 수 있고, 이러한 모든 개질 및 등가물은 하기 청구의 범위에 의해 한정된 개시내용의 범위내에 있는 것으로 여겨진다.Although the present disclosure has been described and described in an illustrative manner, it is not intended to limit the details presented, as various modifications and substitutions may be made in any manner without departing from the scope and spirit of the disclosure. As such, further modifications and equivalents of the disclosures disclosed herein may be performed by one skilled in the art using only routine experimentation, and all such modifications and equivalents are within the scope of the disclosure as defined by the following claims. Is considered.
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Families Citing this family (21)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7883898B2 (en) * | 2007-05-07 | 2011-02-08 | General Electric Company | Method and apparatus for measuring pH of low alkalinity solutions |
| DE102008050092A1 (en) | 2008-10-06 | 2010-04-08 | Hach Lange Gmbh | Mobile water analysis arrangement |
| EP2596347B1 (en) * | 2010-07-22 | 2017-09-06 | Hach Company | Alkalinity analysis using a lab-on-a-chip |
| US9228986B2 (en) | 2010-08-03 | 2016-01-05 | General Electric Company | Simultaneous determination of multiple analytes in industrial water system |
| CA2726064C (en) | 2010-12-21 | 2014-03-11 | Nutriag Ltd. | Agricultural composition comprising ph sensitive agricultural chemicals and organic ph buffer |
| US10605710B2 (en) | 2013-09-30 | 2020-03-31 | Ge Healthcare Bio-Sciences Ab | Method for preparation of liquid mixtures |
| CN103698287B (en) * | 2013-12-19 | 2015-09-23 | 山东省科学院海洋仪器仪表研究所 | For detecting the dim light signal detection device of seawater pH value |
| RU2573453C1 (en) * | 2014-08-14 | 2016-01-20 | Федеральное государственное бюджетное образовательное учреждение высшего профессионального образования "Ивановский государственный энергетический университет имени В.И. Ленина" (ИГЭУ) | METHOD OF DETERMINING pH OF LOW-BUFFER MAXIMALLY DILUTED CONDENSATE-TYPE AQUEOUS SOLUTIONS |
| CN104237229B (en) * | 2014-08-22 | 2016-08-24 | 天津商业大学 | PH value test fluid and preparation method thereof |
| RU2578045C1 (en) * | 2014-11-06 | 2016-03-20 | Федеральное государственное бюджетное образовательное учреждение высшего профессионального образования "Ивановский государственный энергетический университет имени В.И. Ленина" (ИГЭУ) | METHOD FOR AUTOMATIC ADJUSTMENT OF pH OF CIRCULATION WATER OF COOLING LOOP OF ELECTRIC GENERATOR STATOR OF STEAM TURBINE |
| CN107110771A (en) * | 2014-11-07 | 2017-08-29 | 水透镜公司 | Composition, apparatus and method for the basicity that determines analyte solution |
| CN106338511A (en) * | 2016-09-18 | 2017-01-18 | 国网福建省电力有限公司 | Device and method for automatically testing acid value of insulation paper for transformer |
| CN107703019A (en) * | 2017-09-08 | 2018-02-16 | 瓮福达州化工有限责任公司 | Potassium content detection method in a kind of Diammonium phosphate (DAP) of type containing potassium |
| CN107703254B (en) * | 2017-09-14 | 2020-09-29 | 中国神华能源股份有限公司 | Method for detecting whether pH value of ammonium nitrate solution in emulsion explosive is qualified or not |
| RU179664U1 (en) * | 2018-01-30 | 2018-05-22 | Марат Габдулгазизович Бикмуллин | Device for automatically determining the pH of a solution |
| CN110412023A (en) * | 2018-04-27 | 2019-11-05 | 大连理工大学 | A kind of kit and its application method of Fast Evaluation compost maturity |
| CN109632674A (en) * | 2019-01-29 | 2019-04-16 | 厦门鲎试剂生物科技股份有限公司 | A kind of method of test sample pH value |
| JP7415437B2 (en) * | 2019-10-25 | 2024-01-17 | 三浦工業株式会社 | How to adjust the pH of boiler water |
| FR3105424B1 (en) * | 2019-12-23 | 2022-01-14 | Commissariat Energie Atomique | Methods for determining the acidity of an acidic aqueous solution |
| RU2735487C1 (en) * | 2020-03-13 | 2020-11-03 | Лариса Васильевна Атрепьева | Method of studying active reaction of medium for online monitoring of water bodies and hydraulic structures |
| JP7427519B2 (en) | 2020-04-28 | 2024-02-05 | オルガノ株式会社 | pH measurement system and pH measurement method |
Family Cites Families (107)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| BE792465A (en) | 1971-12-09 | 1973-03-30 | Atomic Energy Commission | PERFECTED ROTOR FOR ROTARY PHOTOMETRIC ANALYZER, ESPECIALLY SUITABLE IN WEIGHTNESS CONDITIONS |
| US3998878A (en) | 1975-11-05 | 1976-12-21 | Boise Cascade Corporation | Selectively separating oxalic, tartaric, glyoxylic and erythronic acids from aqueous solutions containing the same |
| JPS5672845A (en) | 1979-11-19 | 1981-06-17 | Hitachi Ltd | Detecting apparatus of examination position of sample |
| JPS56104248A (en) | 1980-01-25 | 1981-08-19 | Kurita Water Ind Ltd | Method and apparatus for measuring anionic polymer concentration |
| US4323536A (en) | 1980-02-06 | 1982-04-06 | Eastman Kodak Company | Multi-analyte test device |
| JPS5853758A (en) | 1981-09-28 | 1983-03-30 | Wako Pure Chem Ind Ltd | Magnesium determining reagent |
| US4514504A (en) | 1983-07-22 | 1985-04-30 | Rohm And Haas Company | Monitoring method for polyacrylic acids in aqueous systems |
| US4894346A (en) | 1983-10-11 | 1990-01-16 | Calgon Corporation | Method for the colorimetric determination of polycarboxylates in aqueous systems |
| US5032526A (en) | 1983-10-11 | 1991-07-16 | Calgon Corporation | Method for the colorimetric determination of sulfonates in aqueous systems |
| US5164598A (en) | 1985-08-05 | 1992-11-17 | Biotrack | Capillary flow device |
| US4756884A (en) | 1985-08-05 | 1988-07-12 | Biotrack, Inc. | Capillary flow device |
| US4857453A (en) | 1987-04-07 | 1989-08-15 | Syntex (U.S.A.) Inc. | Immunoassay device |
| US5005572A (en) | 1988-02-26 | 1991-04-09 | Brigham & Women's Hospital | CO2 indicator and the use thereof to evaluate placement of tracheal tubes |
| SU1567960A1 (en) * | 1988-03-15 | 1990-05-30 | Московский энергетический институт | Device for measuring ph at high pressures and temperature |
| SU1578597A1 (en) * | 1988-06-01 | 1990-07-15 | МГУ им.М.В.Ломоносова | Method of determining isoeletric point of albumen |
| US4877586A (en) | 1988-07-27 | 1989-10-31 | Eastman Kodak Company | Sliding test device for assays |
| US5234813A (en) | 1989-05-17 | 1993-08-10 | Actimed Laboratories, Inc. | Method and device for metering of fluid samples and detection of analytes therein |
| JPH0816649B2 (en) * | 1989-10-13 | 1996-02-21 | 富士写真フイルム株式会社 | Liquid analysis calibration method |
| EP0432642B1 (en) | 1989-12-15 | 1998-06-17 | F. Hoffmann-La Roche Ag | Reagent composition, methods and kits for quantification of magnesium or calcium and magnesium |
| US5094752A (en) | 1990-02-09 | 1992-03-10 | Davis Water & Waste Industries, Inc. | Aerobic wastewater treatment with alkalinity control |
| US5116759A (en) | 1990-06-27 | 1992-05-26 | Fiberchem Inc. | Reservoir chemical sensors |
| IE904444A1 (en) | 1990-12-10 | 1992-06-17 | Stephen J Harris | Ion-selective electrodes |
| US5593850A (en) | 1991-08-30 | 1997-01-14 | Nalco Chemical Company | Monitoring of industrial water quality using monoclonal antibodies to polymers |
| US5290705A (en) | 1992-01-13 | 1994-03-01 | R. E. Davis Chemical Corporation | Speciman support for optical analysis |
| US5599913A (en) | 1992-08-12 | 1997-02-04 | Harris; Stephen J. | Chromoionophores, optical sensors containing them and a method for determining the presence of alkali metal cations or of a base |
| US5354692A (en) | 1992-09-08 | 1994-10-11 | Pacific Biotech, Inc. | Analyte detection device including a hydrophobic barrier for improved fluid flow |
| GB9302903D0 (en) | 1993-02-13 | 1993-03-31 | Univ Strathclyde | Detection system |
| US5342787A (en) | 1993-03-24 | 1994-08-30 | Rohm And Haas Company | Method for solubilizing silica |
| US5504573A (en) | 1993-10-13 | 1996-04-02 | Man-Gill Chemical Company | Apparatus and method for analyzing particles deposited on a substrate using substantially continuous profile data |
| US5470710A (en) | 1993-10-22 | 1995-11-28 | University Of Utah | Automated hybridization/imaging device for fluorescent multiplex DNA sequencing |
| US5478751A (en) | 1993-12-29 | 1995-12-26 | Abbott Laboratories | Self-venting immunodiagnositic devices and methods of performing assays |
| US5389548A (en) | 1994-03-29 | 1995-02-14 | Nalco Chemical Company | Monitoring and in-system concentration control of polyelectrolytes using fluorochromatic dyes |
| ATE176048T1 (en) * | 1994-05-02 | 1999-02-15 | Novartis Ag | OPTICAL SENSOR SYSTEM FOR DETERMINING PH VALUES AND IONIC STRENGTH |
| CA2204912C (en) | 1994-11-10 | 2005-01-04 | David Sarnoff Research Center, Inc. | Liquid distribution system |
| US5645799A (en) | 1995-03-06 | 1997-07-08 | Nalco Chemical Company | Apparatus for a continuous polymer dosage optimization and waste water analysis system |
| US5705394A (en) | 1995-04-17 | 1998-01-06 | Nalco Chemical Company | Tagged epichlorohydrin-dimethylamine copolymers for use in wastewater treatment |
| US5790627A (en) | 1995-09-20 | 1998-08-04 | Research Development Corp. | Method and apparatus for observing a specimen using an X-ray microscope |
| US5747342A (en) | 1995-10-31 | 1998-05-05 | Calgon Corporation | Methods and apparatus for monitoring and controlling PH phosphate and sodium to phosphate ratio in boiler systems operating with captive alkalinity |
| US5736405A (en) | 1996-03-21 | 1998-04-07 | Nalco Chemical Company | Monitoring boiler internal treatment with fluorescent-tagged polymers |
| CA2253710A1 (en) | 1996-04-25 | 1997-10-30 | Spectrametrix Inc. | Analyte assay using particulate labels |
| US5772894A (en) | 1996-07-17 | 1998-06-30 | Nalco Chemical Company | Derivatized rhodamine dye and its copolymers |
| US6113855A (en) | 1996-11-15 | 2000-09-05 | Biosite Diagnostics, Inc. | Devices comprising multiple capillarity inducing surfaces |
| WO1998038510A2 (en) | 1997-02-28 | 1998-09-03 | Burstein Laboratories, Inc. | Laboratory in a disk |
| US6046052A (en) | 1997-05-06 | 2000-04-04 | Ortho Clinical Diagnostics, Inc. | Dry analytical elements for the determination of protein |
| US5958788A (en) | 1997-05-28 | 1999-09-28 | Nalco Chemical Company | Luminol tagged polymers for treatment of industrial systems |
| US5948695A (en) | 1997-06-17 | 1999-09-07 | Mercury Diagnostics, Inc. | Device for determination of an analyte in a body fluid |
| DE69829977T2 (en) | 1997-08-18 | 2005-10-06 | Novartis Ag | OPTICAL CO2 SENSOR |
| DE69731629T2 (en) | 1997-09-11 | 2005-11-03 | Randox Laboratories Ltd., Crumlin | Method and device for image analysis |
| US6011882A (en) | 1997-10-16 | 2000-01-04 | World Precision Instruments, Inc. | Chemical sensing techniques employing liquid-core optical fibers |
| JP2001520892A (en) | 1997-10-27 | 2001-11-06 | アイデックス・ラボラトリーズ・インコーポレーテッド | Analysis apparatus and method for identifying analyte in solution |
| FI107080B (en) | 1997-10-27 | 2001-05-31 | Nokia Mobile Phones Ltd | measuring device |
| US6893877B2 (en) | 1998-01-12 | 2005-05-17 | Massachusetts Institute Of Technology | Methods for screening substances in a microwell array |
| US6051437A (en) | 1998-05-04 | 2000-04-18 | American Research Corporation Of Virginia | Optical chemical sensor based on multilayer self-assembled thin film sensors for aquaculture process control |
| GB9809943D0 (en) | 1998-05-08 | 1998-07-08 | Amersham Pharm Biotech Ab | Microfluidic device |
| GB9815002D0 (en) | 1998-07-11 | 1998-09-09 | Jna Ltd | Formulations |
| US6558320B1 (en) | 2000-01-20 | 2003-05-06 | Medtronic Minimed, Inc. | Handheld personal data assistant (PDA) with a medical device and method of using the same |
| US6143246A (en) | 1998-08-18 | 2000-11-07 | Biochem Technology, Inc. | Apparatus for measuring ammonia in biochemical processes |
| CN1348396A (en) | 1999-03-19 | 2002-05-08 | 金克克国际有限公司 | Multi-through hole testing plate for high throughput screening |
| US6214627B1 (en) | 1999-03-26 | 2001-04-10 | Nalco Chemical Company | Rapid colorimetric method for measuring polymers in aqueous systems |
| ITBO990179A1 (en) | 1999-04-16 | 2000-10-16 | Technogym Srl | TELECOMMUNICATIONS SYSTEM FOR THE EXCHANGE OF PHYSIOLOGICAL STATUS BETWEEN A PHYSICAL PERSON AND AN INFORMATION SYSTEM. |
| EP1208150A4 (en) | 1999-06-11 | 2005-01-26 | Sydney Hyman | Image making medium |
| WO2001007889A2 (en) | 1999-07-27 | 2001-02-01 | Cellomics, Inc. | Miniaturized cell array methods and apparatus for cell-based screening |
| US6648820B1 (en) | 1999-10-27 | 2003-11-18 | Home-Medicine (Usa), Inc. | Medical condition sensing system |
| US6241788B1 (en) | 1999-11-16 | 2001-06-05 | Betzdearborn Inc. | Method of stabilizing dye solutions and stabilized dye compositions |
| US6676903B2 (en) | 2001-07-30 | 2004-01-13 | General Electric Company | Apparatus and method for spatially detecting or quantifying chemical species |
| US6331438B1 (en) | 1999-11-24 | 2001-12-18 | Iowa State University Research Foundation, Inc. | Optical sensors and multisensor arrays containing thin film electroluminescent devices |
| US6379969B1 (en) | 2000-03-02 | 2002-04-30 | Agilent Technologies, Inc. | Optical sensor for sensing multiple analytes |
| US6360585B1 (en) | 2000-03-06 | 2002-03-26 | General Electric Company | Method and apparatus for determining chemical properties |
| WO2001088050A2 (en) | 2000-05-18 | 2001-11-22 | Henkel Loctite Corporation | Adhesive compositions for bonding passive substrates such as magnesium alloys |
| WO2001094921A2 (en) | 2000-06-09 | 2001-12-13 | The Johns Hopkins University | A pH SENSOR SYSTEM AND METHOD FOR USING SAME |
| AU9658801A (en) | 2000-10-04 | 2002-04-15 | Insulet Corp | Data collection assembly for patient infusion system |
| EP1331999A2 (en) | 2000-11-03 | 2003-08-06 | Clinical Micro Sensors, Inc. | Devices and methods for biochip multiplexing |
| US6645142B2 (en) | 2000-12-01 | 2003-11-11 | Optiscan Biomedical Corporation | Glucose monitoring instrument having network connectivity |
| US6627177B2 (en) | 2000-12-05 | 2003-09-30 | The Regents Of The University Of California | Polyhydroxyl-substituted organic molecule sensing optical in vivo method utilizing a boronic acid adduct and the device thereof |
| JP4319363B2 (en) | 2001-01-15 | 2009-08-26 | 富士フイルム株式会社 | Negative type image recording material |
| AU2002258528A1 (en) | 2001-03-14 | 2002-09-24 | Burnstein Technologies, Inc. | Methods of decreasing non-specific binding in dual bead assays and system apparatus for detecting medical targets |
| JP2005233974A (en) | 2001-03-21 | 2005-09-02 | Olympus Corp | Biochemical inspection method |
| US6572902B2 (en) | 2001-04-25 | 2003-06-03 | Advanced H2O, Inc. | Process for producing improved alkaline drinking water and the product produced thereby |
| US6591124B2 (en) | 2001-05-11 | 2003-07-08 | The Procter & Gamble Company | Portable interstitial fluid monitoring system |
| FR2825926A1 (en) * | 2001-06-14 | 2002-12-20 | Sod Conseils Rech Applic | Use of new and known imidazole derivatives as sodium channel modulators used for treating e.g. pain, epilepsy, cardiac rhythm disorders, neurodegeneration, depression, irritable bowel syndrome, and diabetic retinopathies |
| US7169578B2 (en) | 2001-07-27 | 2007-01-30 | Surface Logix, Inc. | Cell isolation and screening device and method of using same |
| AU2002321531B2 (en) * | 2001-08-24 | 2007-12-13 | Sensortec Limited | Methods for producing highly sensitive potentiometric sensors |
| US6898531B2 (en) * | 2001-09-05 | 2005-05-24 | Perlegen Sciences, Inc. | Algorithms for selection of primer pairs |
| WO2003064996A2 (en) | 2002-01-31 | 2003-08-07 | Burstein Technologies, Inc. | Bio-safe dispenser and optical analysis disc assembly |
| US20030157586A1 (en) | 2002-02-21 | 2003-08-21 | Martin Bonde | Device and method for conducting cellular assays using multiple fluid flow |
| JP2004028775A (en) | 2002-06-25 | 2004-01-29 | Olympus Corp | Genetic testing apparatus and method for detecting using the same |
| US6794671B2 (en) | 2002-07-17 | 2004-09-21 | Particle Sizing Systems, Inc. | Sensors and methods for high-sensitivity optical particle counting and sizing |
| KR100480338B1 (en) | 2002-08-08 | 2005-03-30 | 한국전자통신연구원 | Microfluidic devices for the controlled movements of solution |
| JP3908135B2 (en) | 2002-09-09 | 2007-04-25 | オリンパス株式会社 | Image processing method for biochemical examination |
| US7008795B2 (en) | 2002-09-20 | 2006-03-07 | Mitsubishi Electric Research Labs, Inc. | Multi-way LED-based chemochromic sensor |
| CN1188698C (en) * | 2002-11-02 | 2005-02-09 | 中国石油化工股份有限公司 | Device and method of measuring PH value |
| GB2408330B (en) * | 2003-11-22 | 2008-12-03 | Advanced Gel Technology Ltd | Polymeric materials comprising pH indicators for use in wound dressings |
| US7524455B2 (en) | 2003-11-24 | 2009-04-28 | General Electric Company | Methods for deposition of sensor regions onto optical storage media substrates and resulting devices |
| US7456968B2 (en) | 2003-11-24 | 2008-11-25 | General Electric Company | Sensor system and methods for improved quantitation of environmental parameters |
| US7132550B2 (en) | 2003-11-25 | 2006-11-07 | Eastman Kodak Company | Process for the preparation of cyanine dyes with polysulfonate anions |
| US20050133697A1 (en) | 2003-12-23 | 2005-06-23 | Potyrailo Radislav A. | Sensor devices containing co-polymer substrates for analysis of chemical and biological species in water and air |
| DE102004013161B4 (en) | 2004-03-17 | 2008-04-10 | microTec Gesellschaft für Mikrotechnologie mbH | Microfluidic chip |
| WO2006076008A2 (en) | 2004-04-26 | 2006-07-20 | Massachusetts Institute Of Technology | Neural stimulation device employing renewable chemical stimulation |
| ATE486563T1 (en) | 2004-06-15 | 2010-11-15 | Procter & Gamble | SYSTEM FOR EVALUATION OF THE PH VALUE AND BUFFER CAPACITY OF MOISTURE CONTAINING CLEANING ITEMS |
| US20060029516A1 (en) | 2004-08-09 | 2006-02-09 | General Electric Company | Sensor films and systems and methods of detection using sensor films |
| US7288414B2 (en) | 2005-04-19 | 2007-10-30 | Specialty Assays, Inc. | Use of phosphonazo III for the measurement of calcium, magnesium and sodium in analytical samples |
| US7723120B2 (en) * | 2005-10-26 | 2010-05-25 | General Electric Company | Optical sensor array system and method for parallel processing of chemical and biochemical information |
| BRPI0619273A2 (en) * | 2005-10-26 | 2011-09-20 | Gen Electric | METHODS AND SYSTEMS FOR THE PROVISION OF FLUID SAMPLES FOR SENSORS GROUPS |
| US7807473B2 (en) | 2005-10-26 | 2010-10-05 | General Electric Company | Material compositions for sensors for determination of chemical species at trace concentrations and method of using sensors |
| US8133741B2 (en) | 2005-10-26 | 2012-03-13 | General Electric Company | Methods and systems for delivery of fluidic samples to sensor arrays |
| US20070092972A1 (en) | 2005-10-26 | 2007-04-26 | General Electric Company | Self-contained phosphate sensors and method for using same |
| US7883898B2 (en) | 2007-05-07 | 2011-02-08 | General Electric Company | Method and apparatus for measuring pH of low alkalinity solutions |
-
2007
- 2007-05-07 US US11/800,746 patent/US7883898B2/en not_active Expired - Fee Related
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- 2008-04-15 AU AU2008247975A patent/AU2008247975B2/en not_active Ceased
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| RU2009145112A (en) | 2011-06-20 |
| CA2685677A1 (en) | 2008-11-13 |
| CA2685677C (en) | 2017-01-10 |
| JP2010527001A (en) | 2010-08-05 |
| NZ580942A (en) | 2011-05-27 |
| JP5221646B2 (en) | 2013-06-26 |
| TWI449896B (en) | 2014-08-21 |
| EP2145174A1 (en) | 2010-01-20 |
| US7883898B2 (en) | 2011-02-08 |
| RU2456578C2 (en) | 2012-07-20 |
| US20080280373A1 (en) | 2008-11-13 |
| CN101675331B (en) | 2012-06-27 |
| US20110217213A1 (en) | 2011-09-08 |
| CL2008001286A1 (en) | 2008-12-26 |
| EP2145174B1 (en) | 2019-02-13 |
| BRPI0809737A2 (en) | 2014-10-14 |
| AU2008247975A1 (en) | 2008-11-13 |
| US20110091985A1 (en) | 2011-04-21 |
| KR101462295B1 (en) | 2014-11-14 |
| MX2009012072A (en) | 2009-11-19 |
| TW200912285A (en) | 2009-03-16 |
| HK1142132A1 (en) | 2010-11-26 |
| MY151097A (en) | 2014-04-15 |
| US8148166B2 (en) | 2012-04-03 |
| US8076153B2 (en) | 2011-12-13 |
| WO2008137260A1 (en) | 2008-11-13 |
| AR066368A1 (en) | 2009-08-12 |
| AU2008247975B2 (en) | 2013-04-18 |
| CN101675331A (en) | 2010-03-17 |
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